WO2007010878A1 - Membrane microporeuse multicouche constituée de polyoléfines et séparateur pour batterie - Google Patents

Membrane microporeuse multicouche constituée de polyoléfines et séparateur pour batterie Download PDF

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Publication number
WO2007010878A1
WO2007010878A1 PCT/JP2006/314106 JP2006314106W WO2007010878A1 WO 2007010878 A1 WO2007010878 A1 WO 2007010878A1 JP 2006314106 W JP2006314106 W JP 2006314106W WO 2007010878 A1 WO2007010878 A1 WO 2007010878A1
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WIPO (PCT)
Prior art keywords
microporous membrane
polyethylene
polyolefin
polypropylene
mass
Prior art date
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PCT/JP2006/314106
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English (en)
Japanese (ja)
Inventor
Shintaro Kikuchi
Kotaro Takita
Koichi Kono
Original Assignee
Tonen Chemical Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tonen Chemical Corporation filed Critical Tonen Chemical Corporation
Priority to CN200680025849.8A priority Critical patent/CN101223031B/zh
Priority to US11/995,487 priority patent/US9431642B2/en
Priority to KR1020087001717A priority patent/KR101280342B1/ko
Priority to ES06781131.5T priority patent/ES2438738T3/es
Priority to CA2615495A priority patent/CA2615495C/fr
Priority to JP2007526004A priority patent/JP5202949B2/ja
Priority to EP06781131.5A priority patent/EP1905586B1/fr
Publication of WO2007010878A1 publication Critical patent/WO2007010878A1/fr
Priority to US15/216,445 priority patent/US20160329609A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
    • B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/262—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/002—Methods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0021—Combinations of extrusion moulding with other shaping operations combined with joining, lining or laminating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/023—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets using multilayered plates or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/16—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0658—PE, i.e. polyethylene characterised by its molecular weight
    • B29K2023/0683—UHMWPE, i.e. ultra high molecular weight polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0088—Blends of polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0068—Permeability to liquids; Adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
    • B29L2031/3468—Batteries, accumulators or fuel cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/755—Membranes, diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/494—Tensile strength
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a polyolefin multilayer microporous membrane and a battery separator, and more particularly to a polyolefin multilayer microporous membrane and a battery separator excellent in the balance between shutdown characteristics and meltdown characteristics and having good film forming properties.
  • Polyolefin microporous membranes are widely used in applications such as separators for batteries including lithium batteries, diaphragms for electrolytic capacitors, moisture-permeable waterproof clothing, and various filtration membranes.
  • separators for lithium-ion batteries in addition to excellent mechanical properties and permeability, generate heat during abnormalities in order to prevent battery heat generation, ignition, rupture accidents, etc. caused by short circuits or overcharge of external circuits.
  • the ability to stop the battery reaction due to the pores being blocked by [Shutdown (SD) characteristics] and the ability to maintain the shape even at high temperatures and prevent the danger of direct reaction between the cathode and anode materials (dimensions) Stability) is also required.
  • Japanese Patent No. 3235669 describes a low-density polyethylene, an ethylene'butene copolymer or an ethylene'hexene copolymer force as a battery separator having excellent dimensional stability and SD characteristics.
  • a battery separator having at least one first layer comprising: high density polyethylene, ultra high molecular weight polyethylene or polypropylene force; and at least one second layer also having a selected polymer force.
  • Japanese Patent No. 3589778 is a porous membrane that has a high resistance to the extent that current can be interrupted as soon as melting of polyethylene occurs, and is a mixture of polyethylene and polypropylene on both sides of the polypropylene porous membrane.
  • a porous film is disclosed in which the maximum temperature reached when the temperature is raised at a rate of CZ seconds is equal to or lower than the melting point of polyethylene + 20 ° C.
  • WO 2004/089627 is a polyolefin microporous membrane having excellent permeability, high-temperature film strength, high-temperature storage stability and safety, low SD temperature and high short-circuit temperature, and includes polyethylene and polypropylene as essential components.
  • a polypropylene film mixing ratio of at least one surface layer is more than 50% by mass to 95% by mass, and the polyethylene content of the entire film is 50% by mass to 95% by mass.
  • a polyolefin microporous membrane is proposed.
  • a microporous film containing polypropylene on at least one surface layer has a problem of poor film formability and film thickness uniformity. Specifically, when the microporous membrane is slit, polypropylene will fall off, and the amount of powder generated thereby increases, which may cause defects such as black spots in the microporous membrane product. If the film thickness is poor, short circuiting is likely to occur when used as a battery separator, and compression resistance is low. Also inferior. Microporous membranes containing polypropylene on the surface also have the problem of high SD temperatures and slow SD speeds.
  • JP 2002-194132 describes a polypropylene having an MFR of 2.0 or less, a mass average molecular weight, and a Z number average molecular weight. becomes polyethylene and power of 8 to 100, the content of the force mowing Polypropylene has proposed a polyolefin microporous film is 20 mass 0/0 or less.
  • JP 2004-196870 describes a mass average of polyethylene and mass average.
  • the polyolefin microporous film content is 20 mass 0/0 following polypropylene
  • JP 2004-196871 proposes polyethylene and a melting point measured by a scanning differential calorimeter at a temperature rising rate of 3 to 20 ° C./min with a mass average molecular weight of 5 ⁇ 10 5 or more.
  • Japanese Patent Application Laid-Open No. 2002-321323 describes a polyolefin microporous membrane excellent in safety and strength and A three-layer structure of a film AZ film BZ film A or a film BZ film AZ film B is obtained by laminating and integrating a microporous film A containing polyethylene and polypropylene as essential components and a polyethylene microporous film B. Proposed polyolefin microporous membrane.
  • all the examples in this document are examples of a microporous film having a three-layer structure of film AZ film BZ film A, and this document has a three-layer structure of film BZ film AZ film B.
  • microporous membranes There are no examples of microporous membranes. However, this polyolefin microporous membrane does not optimize the properties of polypropylene in the microporous membrane A, so the SD properties may not always be good.
  • an object of the present invention is to provide a polyolefin multilayer microporous membrane and a battery separator that are excellent in the balance between shutdown characteristics and meltdown characteristics and have good film-forming properties.
  • the present inventors have determined that the surface layer on both sides of the polyolefin microporous membrane having at least a three-layer force is a layer having only the strength of polyethylene-based resin.
  • the polyolefin multilayer microporous membrane of the present invention comprises at least three layers, a polyethylene-based resin, a first porous layer that forms at least two surface layers, a polyethylene-based resin, A second porous layer containing at least one layer between both surface layers, and the heat of fusion ( ⁇ H) of the polypropylene measured by a scanning differential calorimeter is 90 J / g or more, Polypropylene content power Poly m in the second porous layer
  • the total amount of ethylene-based resin and polypropylene is 100% by mass, and is 50% by mass or less.
  • the heat of fusion of the polypropylene is preferably 95 J / g or more.
  • Polypropylene The content of is preferably 3 to 45% by mass, more preferably 15 to 45% by mass, with 100% by mass as the total of polyethylene-based resin and polypropylene in the second porous layer. That's right.
  • the ratio of the first porous layer to the second porous layer is preferably such that the solid content mass ratio (first porous layer Z second porous layer) is 90Z10 to 10Z90.
  • a force of 80 to 20 to 40 to 60 is more preferable.
  • the polyethylene resin of the first and second porous layers preferably satisfies the following conditions.
  • the polyethylene-based resin is composed of (a) ultrahigh molecular weight polyethylene, (b) polyethylene other than ultrahigh molecular weight polyethylene, and (c) a composition capable of acting together with ultrahigh molecular weight polyethylene and other polyethylene.
  • (C) Polyethylene composition is more preferred.
  • the polyethylene composition according to the above (1) is an ultrahigh molecular weight polyethylene having a mass average molecular weight of 5 ⁇ 10 5 or more and a mass average molecular weight of 1 ⁇ 10 4 or more to less than 5 ⁇ 10 5 It is preferable to work with polyethylene.
  • the ultrahigh molecular weight polyethylene in the polyethylene composition described in (1) above is an ethylene homopolymer or an ethylene ' ⁇ -olefin copolymer containing a small amount of ⁇ -olefin other than ethylene. Is preferred.
  • Polyethylene having a mass average molecular weight of not less than X 10 4 and less than 5 X 10 5 in the polyethylene composition described in (2) above is high density polyethylene, medium density polyethylene, branched low density polymer.
  • Reethylene, and a group force consisting of a chain low density polyethylene force is preferably at least one selected.
  • High density polyethylene is preferred for polyethylene less than 5 ! /.
  • the polyethylene-based resin has a mass average molecule of 1 ⁇ 10 4 to 1 ⁇ 10 7 Preferably, it has an amount, and Mw / Mn of 5 to 300.
  • the polypropylene of the second porous layer preferably satisfies the following conditions.
  • Weight-average molecular weight of the polypropylene is 1 X 10 4 ⁇ 4 X 10 to 6 in the range of and more preferably a good Mashigu 1 X 10 5 to 9 X 10 5 tool 5 X 10 5 ⁇ 9 X 10 5 and it is particularly preferred arbitrariness.
  • the Mw / Mn of the polypropylene is preferably 1.01 to 100.
  • the melting point of the polypropylene is preferably 155 to 175 ° C, more preferably 163 ° C to 175 ° C.
  • polyolefin multi-layer, microporous membrane of the present invention having the above characteristics, porosity of 25-80%, the air permeability of 2 0 to 400 seconds Z100 cm 3 (converted into a film thickness of 20 ⁇ m), 3,000 mN / Puncture strength of 20 ⁇ m or more, Tensile breaking strength of 100,000 kPa or more, Tensile breaking elongation of 100% or more, Thermal shrinkage of 10% or less (after exposure to 105 ° C for 8 hours), Shutdown of 140 ° C or less Preferably, it has a temperature, a shutdown rate of less than 10 seconds (135 ° C), and a meltdown temperature of more than 160 ° C.
  • the battery separator of the present invention is formed of the above polyolefin multilayer microporous membrane.
  • the polyolefin multilayer microporous membrane of the present invention exhibits low, shutdown temperature, high, shutdown speed, and high meltdown temperature, and is excellent in film formability, mechanical properties, permeability and dimensional stability.
  • RU By using a strong polyolefin multilayer microporous membrane as a battery separator, a battery having excellent safety and productivity such as heat resistance and compression resistance can be obtained.
  • FIG. 1 is a graph showing an example of a typical DSC curve.
  • the polyolefin multilayer microporous membrane of the present invention (hereinafter sometimes simply referred to as “multilayer microporous membrane”) is composed of at least three layers, is composed of polyethylene-based resin, and forms a surface layer on at least both sides. And including polyethylene-based resin and polypropylene, And a second porous layer interposed at least in one layer.
  • the polyethylene-based resin forming the first porous layer is preferably a composition (polyethylene composition) capable of working with ultrahigh molecular weight polyethylene and other polyethylene.
  • Ultra high molecular weight polyethylene has a weight average molecular weight (Mw) of 5 ⁇ 10 5 or more.
  • the ultrahigh molecular weight polyethylene may be not only a homopolymer of ethylene but also an ethylene ′ ⁇ -olefin copolymer containing a small amount of other ⁇ -olefins.
  • Preferred ⁇ -olefins other than ethylene are propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1, otaten-1, vinyl acetate, methyl methacrylate, and styrene.
  • the Mw of ultra high molecular weight polyethylene is preferably 1 ⁇ 10 6 to 15 ⁇ 10 6, more preferably 1 ⁇ 10 6 to 5 ⁇ 10 6 .
  • the ultra high molecular weight polyethylene is not limited to a single material, and may be a mixture of two or more types of ultra high molecular weight polyethylene. Examples of the mixture include a mixture of two or more types of ultrahigh molecular weight polyethylene having different Mw.
  • Polyethylenes other than ultra-high molecular weight polyethylene have a Mw of 1 X 10 4 or more and less than 5 X 10 5 and are also a group of high density polyethylene, medium density polyethylene, branched low density polyethylene and chain low density polyethylene strength. High-density polyethylene is more preferable because at least one of the selected forces is preferred.
  • Polyethylene with an Mw of 1 X 10 4 or more and less than 5 X 10 5 is not only a homopolymer of ethylene but also a copolymer containing a small amount of other ⁇ -olefins such as propylene, butene-1 and hexene-1. But ok. Such a copolymer is preferably produced by a single site catalyst.
  • the polyethylene other than the ultra high molecular weight polyethylene is not limited to a single product, and may be a mixture of two or more types of polyethylene other than the ultra high molecular weight polyethylene.
  • Examples of the mixture include a mixture of two or more types of high-density polyethylenes having different Mw, a mixture of similar medium-density polyethylenes, and a mixture of similar low-density polyethylenes.
  • the content of the ultra high molecular weight polyethylene in the polyethylene yarn composition is preferably 10 to 80% by mass, preferably 1% by mass or more, based on 100% by mass of the entire polyethylene yarn composition. Is more preferred.
  • the polyethylene-based resin not only the above-mentioned polyethylene thread and composition, but also only the above ultrahigh molecular weight polyethylene or only polyethylene other than the above ultra high molecular weight polyethylene may be used as necessary.
  • the polyethylene-based resin may include polyolefins other than polyethylene and polypropylene (hereinafter referred to as "other polyolefins" unless otherwise specified).
  • Polybutene-1, polypentene-1, polyhexene-1 and polyotaten-1 may be not only homopolymers but also other ⁇ -olefin-containing copolymers.
  • the content of the other polyolefin is a whole polyethylene ⁇ more preferably 100 mass 0/0 as 20 wt% or less preferably fixture 10 wt% or less.
  • the Mw of the polyethylene-based resin is not particularly limited, but is preferably 1 X 10 4 to: LX 10 7 and more preferably 5 10 4 to 15 10 6 , Particularly preferred is 1 ⁇ 10 5 to 5 ⁇ 10 6 . If the Mw of the polyethylene ⁇ is a 15 X 10 6 or less, it is easy to melt extrusion.
  • the Mw / Mn of the polyethylene-based resin is not limited, but when the polyethylene-based resin is composed of any of the above-mentioned polyethylene composition, ultrahigh molecular weight polyethylene, or polyethylene other than ultrahigh molecular weight polyethylene, 5 ⁇ 300 is preferred 10 to 100 is more preferred. If Mw / Mn is less than 5, the high molecular weight component is too much and melt extrusion is difficult, and if Mw / Mn exceeds 300, the low molecular weight component is too much and the strength of the laminated microporous film is reduced. Mw / Mn is a measure of molecular weight distribution. The larger this value, the wider the molecular weight distribution.
  • the Mw / Mn of polyethylene (homopolymer and ethylene ′ ⁇ -olefin copolymer) can be adjusted as appropriate by multistage polymerization.
  • the multi-stage polymerization method is preferably a two-stage polymerization in which a high molecular weight polymer component is generated in the first stage and a low molecular weight polymer component is generated in the second stage.
  • Mw / Mn of the polyethylene composition can be appropriately adjusted depending on the molecular weight and mixing ratio of each component.
  • composition of the first porous layer forming both surface layers may be the same or different in each layer, but is preferably the same.
  • the first porous layer may be on the surface layers on both sides, but may be three or more layers as necessary.
  • a first porous layer having a composition different from that of both surface layers may be provided between the surface layers together with the second porous layer.
  • the polyolefin composition for forming the second porous layer contains polyethylene-based resin and polypropylene having a heat of fusion of 90 J / g or more as measured by a scanning differential calorimeter as essential components.
  • the polyethylene-based resin of the second porous layer may be the same as described above.
  • the composition of the polyethylene-based resin of the second porous layer is appropriately selected according to the desired physical properties, which may be the same as or different from the composition of the polyethylene-based resin of the first porous layer. can do
  • Polypropylene must have a heat of fusion ⁇ ⁇ measured by a scanning differential calorimeter (DSC) based on JIS K7122 of 90 J / g or more.
  • DSC scanning differential calorimeter
  • the rate of temperature increase when measuring the heat of fusion is 3-20.
  • Polypropylene heat of fusion ⁇ ⁇ is 90 J / g m
  • Heat of fusion ( ⁇ ⁇ ) is more preferably 95 J / g or more! /.
  • the type of polypropylene is not particularly limited as long as the above-mentioned requirements regarding heat of fusion are satisfied. Any of propylene homopolymer, copolymer of propylene and other ⁇ -olefin and Z or olefin, or a mixture thereof may be used. However, a homopolymer is preferable. As the copolymer, a deviation of a random copolymer or a block copolymer can be used. ⁇ -Olefin preferably has 8 or less carbon atoms.
  • Examples of ⁇ -olefins having 8 or less carbon atoms include ethylene, butene-1, pentene-1, 4-methylpentene-1, otaten-1, vinyl acetate, methyl methacrylate, and styrene.
  • Giolefin has 4 to 14 carbon atoms.
  • Examples of diolefins having a carbon number of ⁇ 14 include butadiene, 1,5-hexagen, 1,7-octadiene, 1,9-decadiene and the like.
  • Mw is more preferably 1 X 10 4 ⁇ 4 X 10 6 are preferably tool 1 X 10 5 ⁇ 9 X 10 5 polypropylene, particularly preferably 5 X 10 5 ⁇ 9 X 10 5 . If a polypropylene having an Mw of less than 1 X 10 4 is used, the meltdown characteristics will deteriorate. On the other hand, when polypropylene of more than 4 ⁇ 10 6 is used, it becomes difficult to knead with the polyethylene resin.
  • the molecular weight distribution (Mw / Mn) of polypropylene is preferably 1.01 to 100, more preferably 1.1 to 50.
  • the melting point of polypropylene is preferably 155 to 175 ° C, more preferably 163 to 175 ° C. Here, the melting point can be measured according to JIS K7121 (the same applies hereinafter).
  • Powdered polypropylene may be used to improve film formability!
  • the powdered polypropylene preferably has an average particle size of 100 to 2,000 ⁇ m and a particle size distribution of 50 to 3,000.
  • the average particle size and the particle size distribution can be measured according to JIS K0069.
  • the polyolefin composition may contain a heat-resistant resin other than polypropylene if necessary!
  • Heat-resistant resin other than polypropylene (hereinafter simply referred to as “heat-resistant resin” unless otherwise specified) is a crystalline resin having a melting point of 150 ° C. or higher (partially crystalline resin) ), And amorphous rosin having a Z or Tg of 150 ° C. or higher.
  • Tg can be measured according to JIS K7121 (the same applies hereinafter).
  • the heat-resistant resin include polyester, polymethylpentene [PMP or TPX (transparent polymer X), melting point: 230 to 245 ° C], polyamide (PA, melting point: 215 to 265 ° C), polyarylene sulfide (PAS), fluorine resin, polystyrene (PS, melting point: 230 ° C), polyvinyl alcohol (PVA, melting point: 220-240 ° C), polyimide (PI, Tg: 280 ° C or higher), polyamideimide (PAI, Tg: 280 ° C), polyethersulfone (PES, Tg: 223 ° C), polyether ether ketone (PEEK, melting point: 334 ° C), polycarbonate (PC, Melting point: 220-240 ° C) Cell mouth acetoacetate (melting point: 220 ° C), cellulose triacetate (melting point: 300 ° C), polysulfone (Tg: 190 °
  • the heat resistant rosin is not limited to one having a single rosin component strength, and may be a plurality of rosin component strengths.
  • the preferred Mw of the heat-resistant resin is a force that varies depending on the type of resin, generally 1 ⁇ 10 3 to 1 ⁇ 10 6, and more preferably 1 10 4 to 7 10 5 .
  • Polyesters include polybutylene terephthalate (PBT, melting point: about 160 to 230 ° C), polyethylene terephthalate (PET, melting point: about 250 to 270 ° C), polyethylene naphthalate (PEN, melting point: 272 ° C). ), Polybutylene naphthalate (PBN, melting point: 245 ° C) and the like PBT is preferred! /.
  • PBT Mw is preferably 2 X 10 4 to 3 X 10 5 ! /.
  • PMP is preferably a homopolymer of 4-methyl-1-pentene! /.
  • Mw of PMP is preferably 3 X 10 5 ⁇ 7 X 1 0 5.
  • PA is preferably at least one selected from the group consisting of polyamide 6 (6-nylon), polyamide 66 (6,6-nylon), polyamide 12 (12-nylon) and amorphous polyamide.
  • Polyphenylene sulfide (PPS, melting point: 285 ° C) is preferred as PAS
  • Fluororesin includes polyvinylidene fluoride (PVDF, melting point: 171 ° C), polytetrafluoroethylene (PTFE, melting point: 327 ° C), tetrafluoroethylene 'perfluoro Alkyl vinyl ether copolymer (PFA, melting point: 310 ° C), tetrafluoroethylene 'hexafluoropropylene' perfluoro (propyl butyl ether) copolymer (EPE, melting point: 295 ° C), tetrafluoro And ethylene'hexafluoropropylene copolymer (FEP, melting point: 275 ° C), ethylene'tetrafluoroethylene copolymer (ETFE, melting point: 270 ° C), and the like. Of these, PVDF is preferred.
  • the content of polypropylene is 50% by mass or less, where the total of polyethylene resin and polypropylene is 100% by mass. If this content exceeds 50% by mass, the SD temperature will increase, the SD speed will decrease, and the film formability will decrease. Specifically, the SD temperature exceeds 140 ° C, or the amount of powder generated due to polypropylene dropping when the multilayer microporous membrane is slit is increased. If the amount of powder generated due to falling off of polypropylene is large, defects such as pinholes and black spots may occur in multilayer microporous membrane products.
  • the content is preferably 3 to 45% by mass, more preferably 15 to 45% by mass. When the content is less than 3% by mass, the meltdown characteristics are deteriorated.
  • the content of the heat-resistant resin is preferably 20% by mass or less, where the total of polyethylene resin, polypropylene and heat-resistant resin is 100% by mass.
  • the second porous layer is usually a single layer, but may be a multilayer if necessary. For example, a plurality of second porous layers having different compositions may be provided.
  • the polyolefin multilayer microporous membrane preferably has a three-layer structure of the first porous layer Z, the second porous layer Z, and the first porous layer.
  • the ratio of the first porous layer to the second porous layer is not limited, but the solid content mass ratio (first porous layer Z second porous layer) is preferably 90Z10 to 10Z90. It is more preferably 80 to 20 to 40 to 60.
  • the first method for producing the polyolefin multilayer microporous membrane of the present invention is: (1) a first melt-kneaded product (first polyolefin solution) obtained by melt-kneading the polyethylene-based resin and the film-forming solvent. (2) preparing the second melt-kneaded product (second polyolefin solution) by melt-kneading the polyolefin composition and the film-forming solvent, and (2) individually preparing the first and second polyolefin solutions.
  • first polyolefin solution obtained by melt-kneading the polyethylene-based resin and the film-forming solvent.
  • step (6) if necessary, (7) Step to stretch the multilayer microporous membrane, (8) Heat treatment step, (9) Crosslinking treatment step by ionizing radiation, (10) Hydrophilization treatment step, etc. May be.
  • a suitable film forming solvent is added to the polyethylene-based resin, and then melted and kneaded to prepare a first polyolefin solution.
  • various additives such as an acid proofing agent, an ultraviolet absorber, an antiblocking agent, a pigment, a dye, and an inorganic filler may be added to the first polyolefin solution as long as the effects of the present invention are not impaired.
  • an acid proofing agent such as an ultraviolet absorber, an antiblocking agent, a pigment, a dye, and an inorganic filler
  • fine silica can be added as a pore-forming agent.
  • a liquid solvent and a solid solvent can be used.
  • the liquid solvent include nonane, decane, decalin, paraxylene, undecane, dodecane, aliphatic hydrocarbons such as liquid paraffin, and mineral oil fractions having boiling points corresponding to these.
  • a non-volatile liquid solvent such as liquid paraffin.
  • the solid solvent preferably has a melting point of 80 ° C. or lower. Examples of such a solid solvent include paraffin wax, seryl alcohol, stearyl alcohol, and dicyclohexyl phthalate.
  • a liquid solvent and a solid solvent may be used in combination.
  • the viscosity of the liquid solvent is preferably in the range of 30 to 500 cSt at a temperature of 25 ° C, more preferably in the range of 30 to 200 cSt. If the viscosity is less than 30 cSt, the polyethylene solution is not uniformly discharged from the die lip, and kneading is difficult. On the other hand, if it exceeds 500 cSt, it is difficult to remove the liquid solvent.
  • Uniform melt-kneading of the first polyolefin solution is not particularly limited, but it is preferably performed in a twin-screw extruder. Melt kneading in a twin screw extruder is suitable for preparing a highly concentrated polyolefin solution.
  • the melt-kneading temperature is preferably within the range of the melting point of the polyethylene composition + 10 ° C to + 100 ° C when the polyethylene-based resin is a polyethylene composition. Specifically, the melt kneading temperature is preferably in the range of 140 to 250 ° C. 170 to 240 More preferably, it is within the range of ° C.
  • the film-forming solvent may be added before the start of kneading, or may be added from the middle of the twin-screw extruder during kneading, but the latter is preferred. In the case of melt kneading, it is preferable to add an acid prevention agent in order to prevent acidity of the polyethylene resin.
  • the blending ratio of the polyethylene-based resin and the film-forming solvent is 10 to 50% by mass, preferably 20 to 50% by mass, with the total of both being 100% by mass. It is -45 mass%.
  • the ratio of the polyethylene-based resin is less than 10% by mass, the swell and neck-in increase at the die exit when the first polyolefin solution is extruded, and the moldability and self-support of the extruded product (gel-like product) are increased. Sex is reduced.
  • the proportion of the polyethylene-based resin exceeds 50% by mass, the moldability of the gel-like molded product is lowered.
  • the second polyolefin solution is prepared by adding the film-forming solvent to the polyolefin composition and then melt-kneading.
  • the second method for preparing a polyolefin solution is that when the polyolefin composition also has polyethylene resin and polypropylene strength, the melt kneading temperature is preferably from the melting point of the polypropylene to the melting point + 70 ° C., and the polyolefin composition is a polyethylene composition.
  • the melt-kneading temperature should be higher than the melting point of crystalline heat-resistant resin or Tg of amorphous heat-resistant resin depending on the type of heat-resistant resin. Is the same as the preparation method of the first polyolefin solution except that is preferable.
  • the melted and kneaded first and second polyolefin solutions are extruded directly or through another extruder, or once cooled and pelletized, and then extruded again through the extruder.
  • a sheet die having a rectangular base is used, but a double cylindrical hollow die, an inflation die, or the like can also be used.
  • the die gap is usually 0.1 to 5 mm, and it is heated to 140 to 250 ° C. during extrusion.
  • the extrusion rate of the heated solution is preferably 0.2 to 15 mZ.
  • the first and second gel sheets are obtained by cooling the extruded gel-like formed bodies having the respective polyolefin solution forces. Cooling to at least the Görch temperature It is preferable to perform at a speed of 50 ° CZ min or more. Cooling to 25 ° C or lower is preferred. In this way, a structure in which the resin phase (the polyethylene-based resin phase in the first gel-like sheet and the polyolefin composition phase in the second gel-like sheet) is microscopically phase-separated by the film-forming solvent. Can be fixed.
  • the cooling rate when the cooling rate is slow, the higher-order structure of the resulting gel-like sheet becomes rough, and the pseudo cell unit forming the gel sheet becomes large, but the cooling rate is fast V and dense cell units.
  • the cooling rate is less than 50 ° CZ, the degree of crystallinity of polyethylene increases, making it difficult to obtain a gel-like sheet suitable for stretching.
  • a cooling method a method of directly contacting cold air, cooling water, or other cooling medium, a method of contacting a roll cooled with a refrigerant, or the like can be used.
  • the obtained first and second gel sheets are stretched in at least a uniaxial direction. Since each gel-like sheet contains a film-forming solvent, it can be stretched uniformly. After heating, each gel sheet is stretched at a predetermined ratio by a tenter method, a roll method, an inflation method, a rolling method, or a combination of these methods.
  • the stretching may be uniaxial stretching or biaxial stretching, but biaxial stretching is preferred.
  • simultaneous biaxial stretching, sequential stretching or multi-stage stretching for example, a combination of simultaneous biaxial stretching and sequential stretching may be misaligned, but simultaneous biaxial stretching is particularly preferred.
  • the draw ratio is preferably 2 times or more, more preferably 3 to 30 times.
  • it is more preferably at least 3 times or more in any direction, and an area magnification of 9 times or more, more preferably an area magnification of 25 times or more. If the area magnification is less than 9 times, stretching is insufficient, and a highly elastic and high strength microporous membrane cannot be obtained. On the other hand, when the area magnification exceeds 400 times, there are restrictions in terms of the stretching apparatus, stretching operation, and the like.
  • the upper limit of the stretching ratio is preferably 10 times in any direction, that is, the area magnification is 100 times.
  • the stretching temperature is preferably the melting point of the polyethylene composition + 10 ° C or less. More preferably, the dispersion temperature is within the range below the melting point. When this stretching temperature exceeds the melting point + 10 ° C., the orientation of molecular chains after stretching deteriorates. On the other hand, if the temperature is lower than the crystal dispersion temperature, the softness of the resin is insufficient, and the film cannot be stretched or stretched at high magnification immediately after stretching.
  • the crystal dispersion temperature is a value obtained by measuring the temperature characteristic of dynamic viscoelasticity based on ASTM D 4065.
  • Ultra high molecular weight polyethylene and other polyethylenes have a crystal dispersion temperature of about 90-100 ° C and a melting point of about 130-140 ° C. Therefore, the stretching temperature is usually in the range of 90 to 140 ° C, preferably in the range of 100 to 130 ° C.
  • a temperature distribution may be provided in the film thickness direction and the film may be stretched to obtain a microporous film having excellent single-layer mechanical strength.
  • the method is specifically described in Japanese Patent No. 3347854.
  • a cleaning solvent is used to remove (wash) the liquid solvent. Since the slag phase (the polyethylene-based slag phase in the first gel-like sheet and the polyolefin yarn and product phase in the second gel-like sheet) is phase-separated from the film-forming solvent, When the solvent is removed, a porous membrane is obtained.
  • the removal (washing) of the liquid solvent can be performed using a known washing solvent.
  • washing solvent examples include saturated hydrocarbons such as pentane, hexane and heptane, chlorinated hydrocarbons such as methylene chloride and tetrachloride carbon, ethers such as jetyl ether and dioxane, ketones such as methylethyl ketone, Chain fluorocarbons such as trifluoromethane, CF and CF
  • a solvent is mentioned. These cleaning solvents have a low surface tension (eg, less than 24 mNZm at 25 ° C). By using a low surface tension cleaning solvent, the network structure forming micropores is prevented from shrinking due to the surface tension at the gas-liquid interface during drying after cleaning, and thus has a high porosity and permeability. A microporous membrane is obtained.
  • Each gel-like sheet after stretching can be washed by a method of immersing in a washing solvent, a method of squeezing the washing solvent, or a combination thereof.
  • the washing solvent is preferably used in an amount of 300 to 30,000 parts by mass with respect to 100 parts by mass of the stretched film.
  • Cleaning with a cleaning solvent is preferably performed until the residual amount of the liquid solvent is less than 1% by mass of the initial addition amount.
  • each polyolefin microporous film obtained by stretching and removing the solvent for film formation is dried by a heat drying method, an air drying method or the like.
  • the drying temperature is preferably below the crystal dispersion temperature of the polyethylene composition, and in particular, it is 5 ° C or more lower than the crystal dispersion temperature. preferable. It is more preferable that the drying be performed until the remaining cleaning solvent is 5% by mass or less, with the microporous membrane being 100% by mass (dry mass). Insufficient drying is preferable because the porosity of the microporous membrane is lowered in the subsequent thermal bonding and the permeability is deteriorated.
  • the dried first and second polyolefin microporous membranes are laminated so that at least both surface layers become the first polyolefin microporous membrane, and at least one second polyolefin microporous membrane is interposed between both surface layers, Join.
  • the dried first polyolefin microporous membrane is bonded to both sides of the second polyolefin microporous membrane.
  • the joining method is not particularly limited, but a thermal joining method is preferable.
  • the heat bonding method include a heat sealing method, an impulse sealing method, an ultrasonic bonding method, and the like, but a heat roll method is preferable, in which the heat sealing method is preferable.
  • it is not limited to the hot roll method.
  • the hot roll method the laminated first and second polyolefin microporous films are passed between a pair of heated rolls or between a heated roll and a cradle and heat sealed.
  • the temperature and pressure at the time of heat sealing are not particularly limited as long as each polyolefin microporous membrane is sufficiently adhered and the characteristics of the obtained multilayer microporous membrane are not deteriorated, and may be set as appropriate.
  • the heat sealing temperature is, for example, 90 to 135 ° C, preferably 90 to 115 ° C.
  • the heat seal pressure is not limited, but is preferably 0.1 to 50 MPa.
  • the multilayer microporous film obtained by bonding is preferably stretched at least in a uniaxial direction.
  • the multilayer microporous membrane can be stretched by a roll method, a tenter method, or the like as described above while heating the multilayer microporous membrane.
  • the multilayer microporous membrane may be stretched uniaxially or biaxially. In the case of biaxial stretching, either simultaneous biaxial stretching or sequential stretching may be used. Biaxial stretching is preferred.
  • the stretching temperature is preferably lower than the melting point of the polyethylene composition of the first porous layer. It is more preferable to set the temperature within the range of the crystal dispersion temperature power or lower than the melting point.
  • the stretching temperature exceeds the melting point, the compression resistance is lowered, and when stretched in the transverse direction (TD), the variation in physical properties (especially air permeability) increases in the sheet width direction.
  • the temperature is lower than the crystal dispersion temperature, the softness of the polyethylene-based resin is insufficient, and the film cannot be stretched immediately and uniformly during stretching.
  • the stretching temperature is usually in the range of 90 to 135 ° C, preferably in the range of 95 to 130 ° C.
  • the stretching ratio of the multilayer microporous membrane in the uniaxial direction is 1.1 to 2.5 times. This further improves the compression resistance of the multilayer microporous membrane.
  • MD longitudinal direction
  • TD direction TD direction
  • the stretching ratios in the MD direction and TD direction may be different from each other in the MD direction and TD direction as long as they are 1.1 to 2.5 times, but are preferably the same.
  • the stretching ratio is more preferably 1.1 to 2.0 times.
  • Heat treatment stabilizes the crystal and makes the lamellar layer uniform.
  • heat setting treatment and Z or heat relaxation treatment may be used.
  • the heat setting treatment is performed within the temperature range of the melting point of the polyethylene composition + 10 ° C or lower, preferably from the crystal dispersion temperature to the melting point. To do.
  • the heat setting treatment is performed by a tenter method, a roll method or a rolling method.
  • the thermal relaxation treatment may be performed using a belt conveyor or an air floating heating furnace.
  • the thermal relaxation treatment is performed at a temperature not higher than the melting point of the polyethylene composition, preferably within a temperature range of not lower than 60 ° C and not higher than 10 ° C. .
  • heat relaxation treatment permeability And a high-strength multilayer microporous membrane with good strength can be obtained. It is also possible to carry out a combination of heat setting and heat relaxation.
  • the multilayer microporous membrane after bonding or stretching may be subjected to a crosslinking treatment by irradiation with ionizing radiation such as ⁇ rays,) 8 rays, ⁇ rays, and electron beams.
  • ionizing radiation such as ⁇ rays,) 8 rays, ⁇ rays, and electron beams.
  • electron beam irradiation an acceleration voltage of 100 to 300 kV is preferred, with an electron dose of 0.1 to 100 Mrad being preferred.
  • the meltdown temperature of the polyethylene multilayer microporous film is increased by the crosslinking treatment.
  • the multilayer microporous membrane after joining or stretching may be hydrophilized!
  • the hydrophilization treatment can be performed by monomer grafting, surfactant treatment, corona discharge or the like.
  • the monomer graph is preferably performed after the crosslinking treatment.
  • any of a nonionic surfactant, a cationic surfactant, an anionic surfactant, or an amphoteric surfactant can be used. Is preferred.
  • the solution is applied to the multi-layer microporous membrane by the doctor blade method by immersing the multi-layer microporous membrane in a solution obtained by dissolving the surfactant in water or a lower alcohol such as methanol, ethanol or isopropyl alcohol.
  • the third production method is different from the first production method in that the stretched first gel sheet and Z or second gel sheet before washing, and / or the first polyolefin after washing.
  • the only difference is that the microporous membrane and the Z or second polyolefin microporous membrane are contacted with a hot solvent, and the other steps are the same. Therefore, only the hot solvent treatment process will be described below.
  • the hot solvent treatment is preferably performed on the stretched first and second gel sheets before washing.
  • the solvent used in the heat treatment the above liquid film-forming solvent is preferable. Above all I prefer moving paraffin.
  • the heat treatment solvent may be the same as or different from the one used to produce the first polyolefin solution or the second polyolefin solution.
  • the thermal solvent treatment method is not particularly limited as long as the gel-like sheet or microporous membrane after stretching can be brought into contact with the thermal solvent.
  • the gel-like sheet or microporous membrane after stretching is directly heated.
  • a method of contacting with a solvent hereinafter, simply referred to as “direct method” unless otherwise specified
  • a method of heating a gel-like sheet or microporous membrane after being brought into contact with a cold solvent hereinafter referred to as “special method”. Unless otherwise noted, it is simply called “indirect method”).
  • the direct method includes a method in which the stretched gel-like sheet or microporous membrane is immersed in a hot solvent, a method in which the hot solvent is sprayed on the stretched gel-like sheet or microporous membrane, a gel-like shape after stretching the hot solvent.
  • a hot solvent is sprayed on the stretched gel-like sheet or microporous membrane, a gel-like shape after stretching the hot solvent.
  • the indirect method includes immersing the stretched gel sheet or microporous membrane in a cold solvent, spraying the cold solvent on the stretched gel sheet or microporous membrane, and stretching the cold solvent to the gel after stretching.
  • the gel sheet or microporous film to which the cold solvent is adhered is applied to a hot sheet, heated in an oven, or immersed in a hot solvent after being applied to the sheet or microporous film. .
  • the temperature of the hot solvent is preferably in the range from the crystal dispersion temperature of the polyethylene composition to the melting point + 10 ° C.
  • the hot solvent temperature is preferably 110 to 140 ° C, more preferably 115 to 135 ° C.
  • the contact time is preferably 0.1 second to 10 minutes, more preferably 1 second to 1 minute. If the hot solvent temperature is lower than the crystal dispersion temperature or the contact time is less than 0.1 seconds, the effect of the hot solvent treatment will hardly improve. On the other hand, if the temperature of the hot solvent is higher than the melting point + 10 ° C. or if the contact time is longer than 10 minutes, the strength of the microporous film is reduced or the microporous film is broken.
  • the stretched gel-like sheet or microporous membrane is treated with a hot solvent, it is washed and the remaining solvent for heat treatment is removed. Since the cleaning method may be the same as the above-mentioned solvent removal method for film formation, the description is omitted. Needless to say, when hot solvent treatment is applied to the stretched gel sheet In this case, the heat treatment solvent can also be removed by performing the film forming solvent removal treatment.
  • the fibrils formed by stretching become a leaf vein shape, and the trunk fibers become relatively thick. Therefore, a microporous membrane having a large pore diameter and excellent strength and permeability can be obtained.
  • “leaf vein-like fibrils” means a state in which the fibrils are composed of thick trunk fibers and fine fiber fibers connected to the outside, and the fine fiber fibers form a complex network structure.
  • the heat-setting treatment before washing may be in the third manufacturing method, not limited to the second manufacturing method. That is, in the third production method, the gel-like sheet before and after the hot solvent treatment and Z or after may be subjected to heat setting treatment.
  • the first and second polyolefin solutions are simultaneously extruded from a die to form a layered extrudate, which is cooled to form a gel-like multilayer sheet.
  • the only difference is that the formed multilayer gel sheet is stretched, the film-forming solvent is removed, and the resulting multilayer microporous film is dried, and the other steps are the same.
  • the stretching method, film forming solvent removal method and drying method may be the same as described above. Therefore, only the process for forming the gel-like multilayer sheet will be described.
  • first and second polyolefin solutions obtained by melt-kneading directly from each extruder or from each die through another extruder. Once cooled and pelletized, a plurality of extrusions are performed again. Extrude simultaneously from the die through the machine. In coextrusion, the first and second polyolefin solutions are combined in layers in a single die and extruded into a sheet (adhesion within the die), or each solution is extruded into a sheet by using separate die forces. Bonding outside (die outside bonding) may be performed, but the former is preferable.
  • either a flat die method or an inflation method may be used.
  • each solution is supplied to separate mold holders of the multilayer die and bonded in layers at the die lip inlet (multiple mold hold method), or each solution is previously added.
  • block method the deviation of the method of combining the layers and supplying them to the die. Since the majority hold method and the block method itself are known, a detailed description thereof will be omitted.
  • known flat dies and inflation dies can be used.
  • the gap of multi-layer flat dies is preferably in the range of 0.1 to 5 mm. Good.
  • the sheet-like solution that has also extruded each die force is pressed by passing it between a pair of rolls.
  • the die is heated to a temperature of 140 to 250 ° C. during extrusion.
  • the extrusion rate of the heated solution is preferably within the range of 0.2 to 15 mZ.
  • the layered extruded product thus obtained is cooled to form a gel-like multilayer sheet.
  • the cooling speed, cooling temperature, and cooling method for the layered extruded product are the same as in the first manufacturing method.
  • the fifth production method differs from the fourth production method only in that the gel-like multilayer sheet after stretching is heat-fixed and then the solvent for film formation is removed, and the other steps are the same. It is.
  • the sixth production method differs from the fourth production method only in that the stretched gel-like multilayer sheet before washing and Z or the multilayer microporous membrane after washing are brought into contact with a hot solvent. This process is the same.
  • the hot solvent treatment method may be the same as the third production method.
  • the polyolefin multilayer microporous membrane obtained by the above method has the following physical properties.
  • air permeability is 20 to 400 seconds Z100 cm 3
  • the battery capacity is increased and the cycle characteristics of the battery are also improved.
  • Air permeability 20 seconds Z100 cm shutdown when the temperature is elevated in the batteries is less than 3 Do sufficiently performed,
  • the multilayer microporous membrane does not have good air permeability.
  • it exceeds 80% when the multilayer microporous membrane is used as a battery separator, the strength becomes insufficient and the risk of short-circuiting the electrodes increases.
  • the puncture strength is less than 3,000 ⁇ 20 / ⁇ ⁇
  • the short circuit of the electrode may occur when the multilayer microporous membrane is incorporated in a battery as a battery separator. Puncture strength is 3,500 m N / 20 ⁇ m or more is preferable.
  • thermal shrinkage ratio after exposure to 105 ° C for 8 hours exceeds 10% in both the longitudinal direction (MD) and the transverse direction (TD), when the multilayer microporous membrane is used as a battery separator, the heat generation of the battery The separator is more contracted, and the possibility that a short circuit occurs at the end portion is increased.
  • the thermal shrinkage rate is preferably 8% or less in both the MD direction and the TD direction.
  • the difference in SD temperature between the first porous layer and the second porous layer is more than 10 ° C, when the multi-layer microporous membrane is used as a lithium battery separator, the shut-off response during overheating decreases.
  • the This difference is preferably within 7 ° C.
  • the shut-off response during overheating decreases when the multilayer microporous membrane is used as a lithium battery separator.
  • the SD speed is preferably 7 seconds or less.
  • the meltdown temperature is preferably 170 ° C or higher.
  • the separator for a battery comprising the above-mentioned polyolefin multilayer microporous membrane preferably has a thickness of 5 to 50 / ⁇ ⁇ , preferably having a thickness of 3 to 200 m, which can be appropriately selected depending on the type of battery. It is particularly preferable to have a film thickness of 10 to 35 ⁇ m.
  • the polyolefin microporous membrane of the present invention is preferably used as a separator for a secondary battery such as a nickel-hydrogen battery, a nickel-powered battery, a nickel-zinc battery, a silver-zinc battery, a lithium secondary battery, or a lithium polymer secondary battery. Particularly, it is preferable to use as a separator for a lithium secondary battery.
  • a lithium secondary battery will be described as an example.
  • a positive electrode and a negative electrode are laminated via a separator, and the separator contains an electrolytic solution (electrolyte).
  • the structure of the electrode is not particularly limited, and may be a known structure. For example, an electrode structure in which disc-shaped positive and negative electrodes are arranged to face each other (coin type), an electrode structure in which flat plate-shaped positive electrodes and negative electrodes are alternately stacked (stacked type), and a stacked strip-shaped positive electrode And an electrode structure in which the negative electrode is wound (winding type).
  • the positive electrode usually has a current collector and a layer formed on the surface thereof and containing a positive electrode active material capable of occluding and releasing lithium ions.
  • the positive electrode active material include transition metal oxides, composite oxides of lithium and transition metals (lithium composite oxides), and inorganic compounds such as transition metal sulfides. Transition metals include V, Mn, Fe, Co, Ni etc. are mentioned.
  • the lithium composite oxide include lithium nickelate, lithium cobaltate, lithium manganate, and a layered lithium composite oxide based on an ⁇ -NaFeO type structure.
  • the negative electrode active material has a current collector and a layer formed on the surface thereof and containing a negative electrode active material.
  • the negative electrode active material include carbonaceous materials such as natural graphite, artificial graphite, coatas, and carbon black.
  • the electrolytic solution is obtained by dissolving a lithium salt in an organic solvent.
  • Lithium salts include LiCIO, LiPF, LiAsF, LiSbF, LiBF, LiCFSO, LiN (CFSO), LiC (CFSO), Li
  • LiAlCl LiAlCl and the like. These may be used alone or as a mixture of two or more.
  • Organic solvents include ethylene carbonate, propylene carbonate, High boiling point and high dielectric constant organic solvents such as rumethyl carbonate, ⁇ -petit-mouth rataton, and low boiling point and low viscosity such as tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, dioxolane, dimethyl carbonate, and jetyl carbonate.
  • Organic solvents are mentioned. These may be used singly or as a mixture of two or more.
  • a high dielectric constant organic solvent has a high viscosity
  • a low viscosity organic solvent has a low dielectric constant. Therefore, it is preferable to use a mixture of both.
  • the separator When the battery is assembled, the separator is impregnated with the electrolytic solution. Thereby, ion permeability can be imparted to the separator (multi-layer microporous membrane). Usually, the impregnation treatment is performed by immersing the multilayer microporous membrane in an electrolyte at room temperature.
  • a positive electrode sheet, a separator made of a multilayer microporous film, and a negative electrode sheet are laminated in this order, and the obtained laminate is wound from one end to form a wound electrode element.
  • a battery can be produced by inserting the obtained electrode element into a battery can, impregnating with the electrolyte solution, and further applying a battery lid serving as a positive electrode terminal provided with a safety valve via a gasket.
  • a mixture was prepared by dry blending 0.2 parts by mass of tetrakis [methylene-3- (3,5-ditertiarybutyl-4-hydroxyphenol) -propionate] methane as an anti-oxidation agent to parts by mass. .
  • the melting point measured for the polyethylene (PE) composition consisting of UHMWPE and HDPE was 135 ° C, and the crystal dispersion temperature was 100 ° C.
  • Mw of UHMWPE and HDPE is gel permeation chromatography under the following conditions.
  • Calibration curve Prepared from a calibration curve obtained using a monodisperse polystyrene standard sample using a predetermined conversion constant.
  • the gel-like sheet was simultaneously biaxially stretched at 115 ° C so that both the longitudinal direction (MD) and the transverse direction (TD) were 5 times.
  • the obtained stretched membrane was fixed to a 20 cm ⁇ 20 cm aluminum frame, immersed in methylene chloride adjusted to 25 ° C., and washed with rocking at 100 rpm for 3 minutes.
  • the obtained membrane was air-dried at room temperature to produce a first polyolefin microporous membrane.
  • the flop propylene homopolymer (PP) polyolefin composition 100 parts by mass consisting of 20 wt% of the heat of fusion of 96 J / g, The mixture was prepared by dry blending 0.2 parts by mass of the above-mentioned anti-oxidation agent.
  • the melting point measured by the polyethylene (PE) composition also having UHMWPE and HDPE strength was 135 ° C, and the crystal dispersion temperature was 100 ° C.
  • the Mw of PP was determined by the GPC method as described above.
  • the polypropylene sample is left in the sample holder of a scanning differential calorimeter (Perkin Elmer, In, DSC-Sy stem7 type) and heat-treated at 190 ° C for 10 minutes in a nitrogen atmosphere. , Cooled to 40 ° C in 10 ° CZ minutes, held at 40 ° C for 2 minutes, and heated to 190 ° C at a rate of 10 ° CZ.
  • the base line and the DSC curve are drawn by drawing a straight line that passes through the point at 85 ° C and the point at 175 ° C on the DSC curve (melting curve) obtained during the heating process.
  • the amount of heat was calculated from the area S of the hatched portion surrounded by.
  • the heat of fusion ⁇ (unit: J / g) was determined by dividing the amount of heat (unit: J) by the mass of the sample (unit: g).
  • Two sheets of the first polyolefin microporous membrane were laminated on both sides of the obtained second polyolefin microporous membrane and joined by passing between a pair of rolls heated to a temperature of 110 ° C (pressure 0.5 G )
  • the obtained multilayer microporous membrane is stretched 1.6 times in the MD direction at a temperature of 110 ° C by a multistage heating roll, and 1.6 times in the TD direction at a temperature of 110 ° C by a tenter stretching machine. It extended
  • UHMWPE30 mass 0/0 and HDPE70 wt% Ca becomes polyethylene composition in the same manner as in Example 1 except that to prepare a first polyolefin microporous membrane with (mp 135 ° C, crystal dispersion temperature 100 ° C), polyolefin A three-layer microporous membrane was prepared.
  • UHMWPE5 mass 0/0, HDPE55 mass 0/0 and PP40 polyolefin composition comprising by weight 0/0 (mp 135 ° C for PE composition comprising UHMWPE and HDPE, the crystal dispersion temperature 100 ° C) using a concentration
  • a second polyolefin solution having a mass of 30% by mass was prepared and a second polyolefin microporous membrane was prepared using the obtained second polyolefin solution.
  • a porous membrane was produced.
  • a polyolefin three-layer microporous membrane was produced in the same manner as in Example 2 except that the membrane was washed.
  • the first and second polyolefin solutions were prepared in separate twin screw extruders in the same manner as in Example 1, and these were fed to each twin screw force three-layer T-die and the first PO solution Z
  • the second PO solution Z was extruded so as to form a molded body laminated in the order of the first PO solution.
  • the extruded molded body was cooled while being drawn with a cooling roll adjusted to 0 ° C. to form a gel-like three-layer sheet.
  • the gel-like three-layer sheet was simultaneously biaxially stretched at 115 ° C so that both the longitudinal direction (MD) and the transverse direction (TD) were 5 times.
  • the obtained stretched gel-like three-layer sheet was washed in the same manner as described above, air-dried, fixed to a tenter, and subjected to a thermal relaxation treatment at 125 ° C for 10 minutes to obtain a polyolefin three-layer microporous membrane (thickness: 24.8 ⁇ m) was produced.
  • a second polyolefin solution containing a PO composition (PO composition A: 15% by mass of UHMW PE, 65% by mass of HDPE and 20% by mass of PP) was prepared in the same manner as in Example 1 except that the concentration was 30% by mass.
  • a polyolefin microporous membrane A for surface layer was produced from the obtained second polyolefin solution in the same manner as in Example 1.
  • PE composition (PO composition B: UHMW PE20 wt% and HDPE80 mass 0/0) to prepare a first polyolefin solution containing. From the obtained first polyolefin solution, a polyolefin microporous membrane B for inner layer was produced in the same manner as in Example 1.
  • a polyolefin three-layer microporous membrane was prepared in the same manner as in Example 1 except that two surface-layer polyolefin microporous membranes A were laminated on both sides of the obtained polyolefin microporous membrane B for inner layer.
  • PE composition (PO composition B: UHMW PE20 wt% and HDPE80 mass 0/0) to prepare a first polyolefin solution containing. From the obtained first polyolefin solution, a polyolefin microporous membrane B for inner layer was produced in the same manner as in Example 1.
  • a polyolefin three-layer microporous membrane was prepared in the same manner as in Example 1 except that two surface-layer polyolefin microporous membranes A were laminated on both sides of the obtained polyolefin microporous membrane B for inner layer.
  • Polyolefin microporous membranes A and B were prepared in the same manner as in Comparative Example 1.
  • a polyolefin microporous membrane was prepared in the same manner as in Example 1 except that the obtained polyolefin microporous membranes A and B were joined one by one.
  • PE composition (PO composition A: UHMWPE20 wt% and HDPE80 mass 0/0) to prepare a first polyolefin solution containing. From the obtained first polyolefin solution, a polyolefin microporous membrane A for surface layer was produced in the same manner as in Example 1.
  • UHMWPE8 mass 0/0, HDPE32 mass 0/0 and PP60 mass 0/0 force becomes polyolefin composition (melting point 135 ° C for PE composition comprising UHMWPE and HDPE, the crystal dispersion temperature 100 ° C) except for using the B
  • a polyolefin solution having a concentration of 25% by mass was prepared.
  • the polyolefin for the inner layer in the same manner as in Example 1.
  • a microporous membrane B was prepared.
  • a polyolefin three-layer microporous membrane was prepared in the same manner as in Example 1 except that two surface-layer polyolefin microporous membranes A were laminated on both sides of the obtained polyolefin microporous membrane B for inner layer.
  • UHMWPE10 mass 0/0, HDPE40 mass 0/0 and PP50 polyolefin composition comprising by weight 0/0 (mp 135 ° C for PE composition comprising UHMWPE and HDPE, the crystal dispersion temperature 100 ° C) except for using A
  • a polyolefin solution having a concentration of 30% by mass was prepared.
  • the draw ratio with respect to the gel-like sheet is 1.6 times X I.
  • a polyolefin microporous membrane A was produced in the same manner as in Example 1 except that the magnification was 0 times (MD X TD).
  • a polyolefin solution having a concentration of 25% by mass was prepared in the same manner as in Example 1 except that only PP was used.
  • a polyolefin microporous membrane B was prepared in the same manner as in Example 1 except that the draw ratio of the gel-like sheet was 1.6 ⁇ 1.0 (MD ⁇ TD).
  • a polyolefin microporous membrane was prepared in the same manner as in Example 1 except that the obtained polyolefin microporous membranes A and B were joined one by one.
  • PE composition (PO composition A: UHMWPE20 wt% and HDPE80 mass 0/0) to prepare a first polyolefin solution containing. From the obtained first polyolefin solution, a polyolefin microporous membrane A for surface layer was produced in the same manner as in Example 1.
  • a polyolefin three-layer microporous membrane was prepared in the same manner as in Example 1 except that two surface-layer polyolefin microporous membranes A were laminated on both sides of the obtained polyolefin microporous membrane B for inner layer.
  • the film thickness was measured with a contact thickness meter at an interval of 5 mm over a length of 30 cm in the transverse direction (TD) at any longitudinal position of the multilayer microporous membrane, and the measured values of the film thickness were averaged.
  • a multilayer microporous membrane with a thickness of T is 2
  • Measurement was performed by ASTM D882 using a strip-shaped test piece having a width of 10 mm.
  • the multilayer microporous membrane was fixed on a plate temperature-controlled at 135 ° C so as to be in surface contact, and the air permeability of a plurality of samples heat-treated with various contact times was measured. From the obtained data, the time (seconds) required for the air permeability to exceed 100,000 seconds Z100 cm 3 (converted to a film thickness of 20 ⁇ m) was determined and used as the SD speed.
  • thermal Z-stress Z-strain measuring device raise the temperature from room temperature at a rate of 5 ° C Zmin while pulling a 10 mm (TD) X 3 mm (MD) test piece in the longitudinal direction of the test piece with a load of 2 g. The temperature at which the film was broken by melting was measured.
  • a reel wound with a multilayer microporous membrane (length: 500 m) is set in a slitting machine, cut in half in the running direction while rewinding it at a speed of 50 m / min, and each slit sheet (length) 500 m) was brought into sliding contact with a fixed bar and then wound on a reel. The powder adhering to the fixing bar was collected and its mass was measured.
  • Example No. Example 1 Example 2
  • Example 3 Example 4 Resin composition
  • MD represents the longitudinal direction
  • TD represents the transverse direction
  • (I) represents the first polyolefin microporous membrane
  • (II) represents the second polyolefin microporous membrane
  • (L) Mw represents a mass average molecular weight
  • MD represents the longitudinal direction
  • TD represents the transverse direction
  • A represents the polyolefin microporous membrane A
  • B represents the polyolefin microporous membrane B.
  • the inner layer contains a polyethylene resin and polypropylene, and the content of polypropylene is 100 mass of the total of the polyethylene resin and polypropylene in the inner layer. %, And the heat of fusion ( ⁇ ) of polypropylene is 90 J / g or more, and polyethylene m on both sides of the film forming the inner layer.
  • the system resin layer Since the system resin layer is provided, it shows a low SD temperature of 136 ° C or less, the difference between the SD temperature of the surface layer and the inner layer is within ° C, shows an SD speed of 5 seconds or less, and 175 ° C or more
  • the film exhibited a high meltdown temperature, a good film forming property with very little polypropylene falling off at the time of slitting, and excellent mechanical properties, permeability and dimensional stability.
  • the membranes of Comparative Examples 1 and 2 contain polypropylene in the outer layer, not the inner layer. Therefore, compared to Examples 1 to 5, the SD temperature is higher and the SD speed is slower. The mechanical strength and dimensional stability were poor as well.
  • the membrane of Comparative Example 2 has a particularly high polypropylene content in the outer layer, so the SD temperature force is as high as 170 ° C, and the SD speed is slow as 45 seconds. It was inferior in nature.
  • the SD temperature force is 70 ° C higher than in Examples 1 to 5, and the SD layer is very slow, 75 seconds.
  • the difference in the SD temperature between the inner layer and the inner layer is as large as 25 ° C.
  • permeability, mechanical strength and dimensional stability were also inferior to the membranes of Examples 1-5.
  • the film of Comparative Example 6 has a meltdown temperature of 159 m because the heat of fusion ( ⁇ H) of polypropylene in the inner layer is less than 90 J / g.
  • the strength was lower than that at ° C and the films of Examples 1 to 5 (meltdown temperature: 175 to 180 ° C).

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  • General Chemical & Material Sciences (AREA)
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Abstract

L’invention concerne une membrane microporeuse multicouche constituée de polyoléfines et composée d'au moins trois couches. Cette membrane microporeuse multicouche constituée de polyoléfines comprend des premières couches poreuses composées chacune d'une résine de polyéthylène et constituant au moins les deux couches de surface et une seconde couche poreuse contenant une résine de polyéthylène et du polypropylène et constituant au moins une couche intercalée entre les deux couches de surface. Cette membrane microporeuse multicouche constituée de polyoléfines est caractérisée en ce que la chaleur de fusion (Hm) du polypropylène telle que mesurée par un calorimètre différentiel à balayage n'est pas inférieure à 90 J/g et en ce que la teneur du polypropylène n'est pas supérieure à 50 % en poids si on prend pour 100 % en poids le total de la résine de polyéthylène et du polypropylène présents dans la seconde couche poreuse.
PCT/JP2006/314106 2005-07-15 2006-07-14 Membrane microporeuse multicouche constituée de polyoléfines et séparateur pour batterie WO2007010878A1 (fr)

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CN200680025849.8A CN101223031B (zh) 2005-07-15 2006-07-14 聚烯烃多层微多孔膜及电池用隔离件
US11/995,487 US9431642B2 (en) 2005-07-15 2006-07-14 Multi-layer microporous polyolefin membrane and battery separator
KR1020087001717A KR101280342B1 (ko) 2005-07-15 2006-07-14 폴리올레핀 다층 미세 다공막 및 전지용 세퍼레이터
ES06781131.5T ES2438738T3 (es) 2005-07-15 2006-07-14 Membrana microporosa multicapa de poliolefina y separador de batería
CA2615495A CA2615495C (fr) 2005-07-15 2006-07-14 Membrane microporeuse multicouche constituee de polyolefines et separateur pour batterie
JP2007526004A JP5202949B2 (ja) 2005-07-15 2006-07-14 ポリオレフィン多層微多孔膜及び電池用セパレータ
EP06781131.5A EP1905586B1 (fr) 2005-07-15 2006-07-14 Membrane microporeuse multicouche constituée de polyoléfines et séparateur pour batterie
US15/216,445 US20160329609A1 (en) 2005-07-15 2016-07-21 Multilayer, microporous polyolefin membrane and battery separator

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JPWO2007010878A1 (ja) 2009-01-29
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US9431642B2 (en) 2016-08-30
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CA2615495C (fr) 2014-02-25
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KR20080028444A (ko) 2008-03-31
CN101223031B (zh) 2014-01-08
CA2615495A1 (fr) 2007-01-25
JP5202949B2 (ja) 2013-06-05
RU2008105739A (ru) 2009-08-20
TWI451969B (zh) 2014-09-11
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